Golf ball material, golf ball and method for preparing golf ball material

ABSTRACT

A golf ball material composed of (A) an oxygen-containing inorganic metal compound in the form of a particulate or a master batch capable of neutralizing at least some of the acid groups in an acid-containing polymer blend, (B) one or more polymer selected from among diene polymers, thermoplastic polymers and thermoset polymers, and (C) an acid-containing polymer is prepared by mixing component A in a blend of components B and C. The golf ball material has a good heat resistance, flowability and processability, and can be used to produce high-performance golf balls having durability, scuff resistance and optimal hardness without a loss of rebound.

CROSS-REFERENCE TO RELATED APPLICATION

This non-provisional application claims priority under 35 U.S.C. §119(a)on Patent Application No. 2004-228901 filed in Japan on Aug. 5, 2004,the entire contents of which are hereby incorporated by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to golf ball materials which have a goodheat stability, flow and processability and from which there can beobtained high-performance golf balls endowed with excellent propertiessuch as rebound and durability. The invention also relates to golf ballswhich include as an essential component therein a molding made from sucha golf ball material, and to methods for preparing such golf ballmaterials.

2. Prior Art

In recent years, ionomer resins have been widely used in cover materialsfor golf balls. Ionomer resins are ionic copolymers of an olefin such asethylene with an unsaturated carboxylic acid such as acrylic acid,methacrylic or maleic acid, in which some of the acid groups areneutralized with metal ions such as sodium, lithium, zinc or magnesium.These resins provide excellent characteristics in terms of durability,rebound and scuff resistance of the ball.

At present, the base resins used in cover materials for golf balls aregenerally ionomer resins, but a variety of modifications have been madeto address the incessant desire by golfers for golf balls having a highrebound and an excellent flight performance.

For example, to improve the rebound and cost characteristics of ionomercover materials, U.S. Pat. Nos. 5,312,857, 5,306,760 and InternationalApplication WO 98/46671 describe cover materials composed of an ionomerresin to which a large amount of a metallic soap has been added.

However, the metallic soap in these cover material undergoesdecomposition and vaporization during injection molding, generating alarge amount of fatty acid gas. As a result, molding defects tend toarise. Moreover, the gas that forms deposits on the surface of themolding, greatly lowering its paintability. The rebound characteristicsobtained with these cover materials do not differ much from thoseprovided by ionomer covers of the same hardness which contain nometallic soap; either the rebound in both cases is about the same or, atmost, only a small positive effect is observable from the inclusion of ametallic soap. Hence, such inclusion does not markedly increase rebound.Moreover, depending on the type of metallic soap used, theprocessability and the rebound characteristics are sometimes greatlycompromised, making the cover material entirely unfit for practical use.

An ionomer for use as a golf ball material has recently been developedin the form of a high rebound resilience material which is in ahomogeneous phase and has an interpenetrating network (IPN) structure.The ionomer is obtained by mixing a first component such as anethylene-(meth)acrylic acid copolymer with a different type ofthermoplastic resin as a second component to form a resin composition,then adding a metal ionic species as a third component to neutralize theacid on the first component dispersed in the resin composition (U.S.Patent Application No. 2004/0044136). However, in this prior-artproduction method, because direct use is made of a solid (powder orgranular material) such as a metal oxide, metal hydroxide or metalcarbonate as the source of the metal ions, and also because a high acidcontent in the first component necessitates the addition of a largeamount of the metal ions required for neutralizing the acid, duringadmixture of the metal ions, poor dispersion sometimes arises, leavingsome of the metal ions unreacted. Moreover, a partial neutralizationreaction (incomplete degree of neutralization) occurs, making itimpossible to achieve the target degree of neutralization in a one-stepreaction within an extruder. Hence, more than one extruder pass is made,which it is feared may lower the physical properties of the resultingionomer material.

SUMMARY OF THE INVENTION

It is therefore an object of the invention, by having a metal ionicspecies bring to completion in one step a reaction which neutralizes theacid within an acid-containing polymer composition to a target degree ofacid neutralization, to provide a golf ball material having a good heatstability, flow and processability from which can be obtainedhigh-performance golf balls endowed with excellent properties such asdurability, scuff resistance and optimal hardness without compromisingrebound. Another object of the invention is to provide a golf ball whichcontains as an essential component a molding made from such a golf ballmaterial. A further object of the invention is to provide a method forpreparing such a golf ball material.

We have discovered that by using (A) a metal ionic species in the formof (A1) ultrafine particles and/or (A2) a master batch, and by blendingthis component A together with an acid-containing polymer blendcomposition prepared using a twin-screw reactor-extruder having akneading disc zone to mix (B) at least one polymer selected from thegroup consisting of diene polymers, thermoplastic polymers and thermosetpolymers with (C) at least one acid-containing polymer having an acidcontent of 0.5 to 30% by weight and selected from the group consistingof olefin-unsaturated carboxylic acid copolymers, olefin-unsaturatedcarboxylic acid-unsaturated carboxylic acid ester terpolymers, andpolymers containing one or more monomer selected from the groupconsisting of unsaturated carboxylic anhydrides, unsaturateddicarboxylic acids and unsaturated dicarboxylic acid half esters, theneutralizing reaction by component A on acids in components B and Cproceeds smoothly, yielding a uniform golf ball material in one step.Also, we have found that this golf ball material has a surprisingly goodthermal stability, flow and processability, making it suitable forinjection molding, and moreover is ideal for producing high-performancegolf balls of excellent properties, including durability, scuffresistance and optimal hardness, without compromising the rebound of thematerial.

In addition, we have discovered that golf balls in which a molding madefrom this golf ball material is used as an essential component, such asa cover material in a two-piece solid golf ball composed of a cover anda cover enclosing the core or a cover material or intermediate layermaterial in a multi-piece solid golf ball composed of a core of at leastone layer, at least one intermediate layer enclosing the core and atleast one cover which encloses the intermediate layer, exhibit anexcellent durability, excellent scuff resistance and optimal hardnesswithout a loss of rebound.

Accordingly, the present invention provides a golf ball materialcomprising; (A) a metal ionic species in at least one form selected fromthe group consisting of (A1) ultrafine particles and (A2) a masterbatch, (B) at least one polymer selected from the group consisting ofdiene polymers, thermoplastic polymers and thermoset polymers, and (C)at least one acid-containing polymer having an acid content of 0.5 to30% by weight and selected from the group consisting ofolefin-unsaturated carboxylic acid copolymers, olefin-unsaturatedcarboxylic acid-unsaturated carboxylic acid ester terpolymers, andpolymers containing one or more monomer selected from the groupconsisting of unsaturated carboxylic anhydrides, unsaturateddicarboxylic acids and half esters thereof; which is obtained bypreparing a polymer blend of component B and component C, then blendingcomponent A together with the polymer blend.

In the golf ball material of the invention, component B is preferably atleast one polymer selected from the group consisting of polyolefinelastomers, polystyrene elastomers, polyacrylate polymers, polyamideelastomers, polyurethane elastomers, polyester elastomers, dienepolymers, polyacetals, epoxy resins, unsaturated polyester resins,silicone resins and ABS resins.

In a preferred aspect of the golf ball material of the invention,component B and component C are blended together in a weight ratio B/Cof 99/1 to 1/99.

In another preferred aspect of the inventive golf ball material,component B is a thermoset polymer, and components B and C are blendedtogether in a weight ratio B/C of 49/51 to 1/99.

In the inventive golf ball material, component B is a polybutadienehaving a cis-1,4 bond content of at least 60%, a 1,2-vinyl bond contentof at most 4%, a Mooney viscosity (ML₁₊₄ (100° C.)) of 35 to 65, aweight-average molecular weight (Mw) of 450,000 to 850,000, and aweight-average molecular weight (Mw) to number-average molecular weight(Mn) ratio of at most 5. The polybutadiene may be used itself or in acomposition of an acid anhydride and a radical crosslinking agent.

In preferred aspects of the golf ball material of the invention,component B may be a polybutadiene and comprises between 1 to 50% byweight of the combined weight of component B and component C in thepolymer blend; component B may be a polyacetal homopolymer or copolymeror both having an impact strength of 35 to 130 J/m and a flexuralmodulus of 2.50 to 3.10 GPa; and component B may be a polyacetal andcomprises between 1 to 50% by weight of the combined weight of componentB and component C in the polymer blend.

In the inventive golf ball material, it is preferable for component A1or component A2 or both to be blended together with the polymer blend ofcomponent B and component C in an amount equivalent to a desired degreeof neutralization of the acid groups in the polymer blend of componentsB and C.

In a preferred aspect of the inventive golf ball material, the metalionic species of component A is in the form of (A1) ultrafine particlesof an oxygen-containing inorganic metal compound having an average sizeof 0.005 to 0.1 μm and a particle size distribution of 0.001 to 1.0 μmin diameter. The particulate oxygen-containing inorganic metal compound(A1) is at least one type selected from the group consisting of lithiumcarbonate, sodium carbonate, potassium carbonate, magnesium carbonate,calcium carbonate, magnesium oxide, zinc oxide and calcium oxide.

In another preferred aspect of the inventive golf ball material, themetal ionic species of component A is in the form of (A2) a master batchof an oxygen-containing inorganic metal compound having an averageparticle size of 0.005 to 50 μm and a particle size distribution of0.001 to 300 μm in diameter. The oxygen-containing inorganic metalcompound in this preferred aspect is preferably at least one selectedfrom the group consisting of lithium carbonate, sodium carbonate,potassium carbonate, magnesium carbonate, zinc carbonate, magnesiumhydroxide, magnesium oxide, calcium hydroxide, calcium oxide and zincoxide. The oxygen-containing inorganic metal compound master batch A2preferably comprises a base polymer material having a melt flow rate ofat least 10 g/10 min and the oxygen-containing inorganic metal compoundin an amount of 20 to 80% by weight of the combined weight of the basepolymer material and the oxygen-containing inorganic metal compound, isprepared at a mixing temperature of 50 to 220° C. using an internalmixer such as a forced feeder-attached twin-screw/single-screw extruderin combination with a compression kneader, a tandem-type extruder, and avent port attached twin-screw extruder.

The present invention also provides a method for preparing a golf ballmaterial composed of (A) a metal ionic species in the form of one orboth (A1) ultrafine particles and (A2) a master batch, (B) at least onepolymer selected from the group consisting of diene polymers,thermoplastic polymers and thermoset polymers, and (C) at least oneacid-containing polymer having an acid content of 0.5 to 30% by weight,selected from the group consisting of olefin-unsaturated carboxylic acidcopolymers, olefin-unsaturated carboxylic acid-unsaturated carboxylicacid ester terpolymers, and polymers containing one or more monomerselected from the group consisting of unsaturated carboxylic anhydrides,unsaturated dicarboxylic acids and half esters thereof, which comprisesthe steps of: (a) preparing a polymer blend of component B and componentC; and (b) using component A1 or component A2 or both components A1 andA2 to carry out in one step a neutralization reaction on the acid groupscontained in the polymer blend of components B and C.

In a preferred aspect of the method of the invention, the neutralizationreaction of the acid-containing polymer blend with component A1 orcomponent A2 or both is carried out in one step by a reaction extrudersuch as a twin-screw extruder having a screw segment configuration akneading disc zone. The twin-screw extruder has a length-to-diameter(LD) ratio of at least 20, and the screw segment configuration has thekneading disc zone of an L/D ratio of 10 to 90% of the total L/D ratio.It is desirable that the discs of the kneading disc zone of thetwin-screw extruder include right-handed kneading discs, left-handedkneading discs, reverse discs, and various neutral discs, it ispreferable that the twin-screw extruder has a screw diameter of at least15 mm, and has a vent port and a vacuum line connected thereto.

In another preferred aspect of the inventive method, the twin-screwextruder may be equipped with a device such as a liquid-droppingapparatus or a pressurized liquid injection pump. The liquid ispreferably a chemical shown by the formula ROH, where R is hydrogen oran alkyl group, and is added in an amount of 0.1 to 10% by weight, basedon the resin extrusion output.

In the method of the invention, it is preferable that the neutralizationreaction in the twin-screw extruder is carried out at a settingtemperature of 110 to 260° C., an extrusion output, for a screw diameter(D) of 32 mm, of 2 to 60 kg/h, if the screw diameter ratio D₁/D₂ (D₁being larger than D₂) is A, the extrusion output on the basis ofscale-up of the twin-screw extruder is proportional to A within a rangeof A^(1.0) to A^(3.0).

The invention additionally provides a golf ball comprising a part madeof the golf ball material of the invention.

The invention provides as well a golf ball wherein the above inventivegolf ball material is used as a cover material in a two-piece solid golfball composed of a cover and a cover surrounding the core.

The invention further provides a golf ball wherein the above inventivegolf ball material is used as a cover material or intermediate layermaterial in a multi-piece solid golf ball composed of a core of at leastone layer, at least one intermediate layer surrounding the core, and atleast one cover surrounding the intermediate layer.

The golf ball materials of the invention and the inventive methods forpreparing such golf ball materials enable the reaction in which acidswithin the acid-containing polymer are neutralized to be brought tocompletion. These golf ball materials thus have a good thermalstability, flow and processability. Moreover, they make it possible toobtain high-performance golf balls which are endowed with excellentproperties, including durability, scuff resistance and optimal hardness,without compromising rebound.

DETAILED DESCRIPTION OF THE INVENTION

The invention is a golf ball material characterized by blending together(A) a finely divided metal ionic species, (B) at least one polymerselected from the group consisting of diene polymers, thermoplasticpolymers and thermoset polymers, and (C) at least one acid-containingpolymer selected from the group consisting of olefin-unsaturatedcarboxylic acid copolymers, olefin-unsaturated carboxylicacid-unsaturated carboxylic acid ester terpolymers, and polymerscontaining one or more monomer selected from the group consisting ofunsaturated carboxylic anhydrides, unsaturated dicarboxylic acids andunsaturated dicarboxylic acid half esters; which golf ball material isobtained by preparing a polymer blend of component B and component C,then blending component A together with the polymer blend.

In the practice of the invention, to avoid the thermal history ofpolymer materials obtained with multiple passes by bringing theneutralization reaction to the target degree of neutralization in onestep and thus prepare a better golf ball material, an oxygen-containinginorganic compound in the form of ultrafine particles (A1) is selectedas the metal ionic species (A) used.

The ultrafine particles (A1) used in the invention preferably have anaverage particle size of from 0.005 to 0.1 μm and a particle sizedistribution of 0.001 to 1.0 μm. Compared with ordinary particlesseveral tens of microns in size, such fine particles have a high surfaceactivity, a good reactivity with acids and a good dispersibility, makingthem highly suitable for the neutralization reaction of the invention.

The metal ionic species (A) may be any suitable oxygen-containinginorganic compound that has previously been used. Generally, when theneutralization reaction on acids in the acid-containing polymercomposition is carried out using the oxygen-containing inorganiccompound directly as is, the unreacted oxygen-containing inorganiccompound forms into and remains as undispersed masses, requiringmultiple passes through an extruder to bring the neutralization reactionto the target degree of neutralization. To illustrate, U.S. PatentApplication No. 2004/0044136 describes an example in which magnesiumhydroxide is used as the metal ionic species and the acid-containingpolymer is passed several times through a twin-screw extruder forneutralization.

The ultrafine particulate oxygen-containing inorganic compound (A1) usedas the metal ionic species (A) is preferably selected from among metaloxides, metal carbonates and metal hydroxides having a low moistureabsorption. The metal ionic species (A) is generally selected from amonggroups IA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIA, VIB, VIIBand VIIIB of the periodic table. Specific, non-limiting, examples of theultrafine particulate oxygen-containing inorganic compound (A1) includelithium carbonate, sodium carbonate, potassium carbonate, magnesiumcarbonate, calcium carbonate, magnesium oxide, zinc oxide, calcium oxideand magnesium hydroxide. These may be used singly or as combinations oftwo or more thereof. The use of these ultrafine particulateoxygen-containing inorganic compounds (A1) in a reaction to neutralizethe acid within the acid-containing polymer composition provides suchadvantages as (i) inducing the reaction to proceed smoothly (because itexhibits a high neutralizing reactivity with acid groups), and (ii) alower manufacturing equipment corrosiveness than metal acetates (whichrelease acetic acid after neutralization).

Alternatively, the metal ionic species (A) can be used in the form of amaster batch (A2) prepared from the oxygen-containing inorganiccompound, in which case the (A2) component may be used in place of or incombination with the above-described ultrafine particulateoxygen-containing inorganic compound (A1). The oxygen-containinginorganic metal compound used to prepare the master batch has an averageparticle size of generally from 0.005 to 50 μm and a particle sizedistribution of generally 0.001 to 300 μm. The average particle sizeneed not be as small as that of the ultrafine particulateoxygen-containing inorganic compound described above. However, if theaverage particle size is too large, the neutralization reaction may notreach completion. On the other hand, if the average particle size is toosmall, poor dispersion may occur during master batch preparation. Asused herein, “average particle size” and “particle size distribution”refer to values obtained by particle size distribution measurement usinga laser diffraction technique (laser diffraction/scattering).

By using the oxygen-containing inorganic compound in the form of amaster batch (A2) (referred to below simply as “master batch (A2)”), theoxygen-containing inorganic metal compound can be uniformly dispersed inthe reaction for neutralizing acids in components B and C of theacid-containing polymer blend, further promoting a uniform reaction andmaking it possible to impart uniformity to the golf ball material. Onthe other hand, if the oxygen-containing inorganic metal compound is notprepared as a master batch and is instead directly blended intocomponents B and C of the above polymer blend, the oxygen-containinginorganic metal compound may be difficult to uniformly disperse in thepolymer composition and may form undispersed masses, resulting in anon-uniform reaction, which may in turn lead to poor uniformity of thegolf ball material. In particular, if an oxygen-containing inorganicmetal compound in the form of a coarse powder is used, undispersedmasses will remain in the golf ball material. It is also possible topromote the reaction and obtain a uniform material by preferentiallypreparing a master batch of an organic acid-free oxygen-containinginorganic metal compound which does not release organic acid followingthe neutralization reaction.

When a master batch (A2) is used, the metal ionic species includedtherein is a metal oxide, metal carbonate or metal hydroxide. The metalion is selected from among groups IA, IB, IIA, IIB, IIIA, IIIB, IVA,IVB, VA, VB, VIA, VIB, VIIB and VIIIB of the periodic table. Specific,non-limiting, examples include lithium carbonate, sodium carbonate,potassium carbonate, magnesium carbonate, zinc carbonate, magnesiumhydroxide, magnesium oxide, calcium hydroxide, calcium oxide and zincoxide. These may be used singly or as combinations of two or morethereof.

The concentration of the above oxygen-containing inorganic metalcompound is generally 10 to 90 wt %, preferably 20 to 80 wt %, and morepreferably 30 to 70 wt %. If the concentration of oxygen-containinginorganic metal compound in the master batch (A2) is too high, themaster batch may have a melt flow rate (MFR) of less than 0.1 g/10 min,which is too low. In such a case, blending the master batch togetherwith components B and C may be detrimental to dispersion of theoxygen-containing inorganic metal compound within the master batch. Onthe other hand, if the concentration is low, a larger amount of themaster batch will be added, allowing the influence of the high MFR basepolymer used in the master batch (particularly ethylene waxes andlow-acid content, high-MFR ethylene polymers, etc.) to emerge, which maymarkedly diminish the physical properties of the golf ball material.

The base polymer material used in the master batch (A2) is preferablyone having a high MFR. Specifically, the base polymer material istypically one having an MFR of preferably at least 10 g/10 min, morepreferably at least 50 g/10 min, and even more preferably at least 100g/10 min. Use can also be made of a liquid wax such as a high-MFRethylene wax, or a low-acid, high-MFR ethylene polymer. Specificexamples include Polyethylene Wax AC5120 (available from Tomen PlasticsCorporation; acrylic acid content, 15 wt %; MFR, >1,000 g/10 min),Nucrel 599 (available from DuPont; methacrylic acid content, 10 wt %;MFR, 450 g/10 min), Nucrel 699 (available from DuPont; methacrylic acidcontent, 11 wt %; MFR, 100 g/10 min), and Nucrel N0200H (available fromDuPont-Mitsui Polychemicals Co., Ltd.; methacrylic acid content, 2 wt %;MFR, 130 g/10 min).

The inventive method of preparing a golf ball material is a process inwhich a reaction to neutralize the acid in an acid-containing polymerblend of at least two different polymers, i.e., component B andcomponent C, is carried out in one step with a metal ionic species (A).To carry out the neutralization reaction in this single step, anextruder for neutralization, and in particular a twin-screw extruderhaving arranged therein a screw segment with a kneading disc zone, isemployed so as to blend in the metal ionic species (A).

The amount of the metal ionic species (A) incorporated is necessarilydetermined by the target degree of neutralization of the acid groupspresent in the acid-containing polymer blend of components B and C. Toomuch may result in an excessive degree of neutralization, lowering themelt flow rate (MFR) of the golf ball material and compromising theprocessability. On the other hand, too little may diminish the physicalproperties of the golf ball material and compromise the reboundresilience and durability of golf balls obtained using the material.

The method of preparing the master batch (A2) may involve the use of anapparatus selected from among twin-screw/single-screw extruders(including kneader-extruders) equipped with a kneader such as a pressurekneader and a force feeder, tandem extruders (consisting of a twin-screwextruder for upstream processing and a vacuum-vented extruder fordownstream processing), and vacuum-vented twin-screw extruders. It ismore preferable either to use a twin-screw/single-screw extruderequipped with a kneader and a force feeder or to use a tandem extruder.Using this equipment, a dry blend of the oxygen-containing inorganiccompound and the base polymer material is fed to a hopper and mixed,then pelletized to give a master batch (A2) having a melt flow rate in arange of 0.1 to 100 g/min. Alternatively, the oxygen-containinginorganic compound and the base polymer material may each be fed toseparate feeders then mixed. The master batch mixing temperature isadjusted within a range of 50 to 220° C., and preferably 80 to 180° C.

The golf ball material of the invention can be obtained by mixing thevarious above components using, for example, an internal mixer such as akneading-type twin-screw extruder, a Banbury mixer, a kneader or a LaboPlastomill (made by Toyo Seiki Seisaku-Sho, Ltd.). The extruder used forpreparing the material is preferably a twin-screw extruder. A twin-screwextruder having features (i) to (v) below is especially preferred.

-   (i) An effective screw length L/D (i.e., screw length-to-diameter    ratio) of at least 20, preferably at least 25, and more preferably    at least 30.-   (ii) A screw segment arrangement such that the L/D ratio of the    kneading disc zone is 10 to 90%, preferably 20 to 80%, and more    preferably 30 to 70%, of the overall L/D. Also, the discs in the    kneading disc zone of the twin-screw extruder include a right-handed    kneading disc, a left-handed kneading disc, a reverse disc, and    various neutral discs.-   (iii) A screw diameter of at least 15 mm.-   (iv) Includes a vent port and a vacuum line connected thereto.-   (v) Equipped with a device for the dropwise addition or pressurized    injection of a liquid.

In the one-step neutralization reaction carried out in the method of theinvention, above components B and C are melt-mixed to form a moltenpolymer composition of components B and C. Next, above-describedcomponent A (i.e., component A1 and/or component A2) is blended into themolten polymer composition, and a liquid may also be added (by injectionunder pressure or by dropwise addition) to promote a reaction in whichat least some of the acid groups present in components B and C of thepolymer composition are neutralized. The liquid in this case ispreferably a compound of the formula ROH, where R represents a hydrogenor an alkyl group. The amount of this liquid added, based on the overallresin extrusion rate, is preferably 0.1 to 10 wt %, more preferably 0.5to 8 wt %, and even more preferably 1.0 to 5.0 wt %.

The heating conditions can be set to, for example, 100 to 250° C.,although melt-mixing is preferably carried out at a temperature whichexceeds both the melting point of component B and the melting point ofcomponent C.

Although the mixing method is not subject to any particular limitation,for better microdispersion of component A it is preferable to firstthoroughly melt-mix components B and C so as to form a polymercomposition of components B and C, then to blend and mix in component A(i.e., component A1 and/or component A2). If additives are to beincluded, the additives may be added and mixed into the compositionfollowing the incorporation of component A.

In the practice of the invention, the acid neutralizing reaction oncomponents B and C of the acid-containing polymer composition by theoxygen-containing inorganic metal compound A1 and/or A2 is carried outin one step. The neutralization reaction in the twin-screw extruder usedfor this purpose is carried out at a temperature setting of 110 to 260°C., preferably 130 to 240° C., and more preferably 170 to 230° C. Theextrusion rate for a screw diameter D of 32 mm is 2 to 60 kg/h,preferably 5 to 50 kg/h, and more preferably 10 to 40 kg/h. Moreover, ifthe screw diameter ratio D₁/D₂ (D₁ being larger than D₂) is A, theextrusion rate during scale-up of the twin-screw extruder isproportional to A within a range of preferably A^(1.0) to A^(3.0), andmore preferably A^(1.5) to A^(2.7).

It is preferable to provide the golf ball material of the invention witha melt flow rate (MFR) within a specific range so as to ensure that ithas flow properties which are particularly suitable for injectionmolding and to improve its processability. Hence, the melt flow rate isgenerally at least 0.1 g/10 min, and preferably at least 0.5 g/10 min,but generally not more than 50 g/10 min, and preferably not more than 30g/10 min. A melt flow rate which is too large or too small maysignificantly reduce the processability. As used herein, “melt flowrate” refers to a measured value obtained in accordance with JIS-K7210at a test temperature of 190° C. and a test load of 21.18N (2.16 kgf).

The golf ball material of the invention has, in Fourier transforminfrared absorption spectroscopic (FT-IR) measurements, an absorptionpeak attributable to carbonyl stretching vibrations at 1690 to 1710 cm⁻¹and an absorption peak attributable to the carboxylate anion stretchingvibrations of a metal carboxylate at 1530 to 1630 cm⁻¹, confirming theneutralization reaction and the presence of ionic crosslinks.

Moldings obtained using the golf ball material of the invention have aShore D hardness of generally at least 50, and preferably at least 52,but generally not more than 75, and preferably not more than 70. If themolding has too high a Shore D hardness, the “feel” of the ball when hitmay diminish significantly. On the other hand, if the Shore D hardnessis too low, the rebound of the ball may decrease.

Component B in the invention is one or more polymer selected from thegroup consisting of diene polymers, thermoplastic polymers and thermosetpolymers. Examples include polymers and polymer compositions composed ofone or more selected from the group consisting of polyolefin elastomers,polystyrene elastomers, polyacrylate polymers, polyamide elastomers,polyurethane elastomers, polyester elastomers, diene polymers,polyacetals, epoxy resins, unsaturated polyester resins, silicone resinsand ABS resins.

If above component B is a diene polymer, polybutadiene is especiallypreferred. This polybutadiene preferably has a cis-1,4 bond content ofat least 60%, a 1,2-vinyl bond content of not more than 4%, a Mooneyviscosity (ML₁₊₄ (100° C.) of 35 to 65, a weight-average molecularweight (Mw) of 450,000 to 850,000, and a weight-average molecular weight(Mw) to number-average molecular weight (Mn) ratio of at most 5.Illustrative examples include polybutadienes prepared using a nickelcatalyst and polybutadienes prepared using a lanthanide series catalyst,of which the latter is preferred.

The polybutadiene serving as component B may be used directly as is.Alternatively, it may be used as a butadiene-containing compositionobtained by mixture with an acid anhydride and a radical generator suchas a peroxide. In addition, component C and the butadiene-containingcomposition are mixed together, following which a neutralizationreaction is carried out using the metal ionic species serving ascomponent A (i.e., component A1 and/or component A2). In this way, atthe same time that metal ion crosslinking is carried out, grafting ofthe acid anhydride occurs and a material having a homogeneous phase onaccount of the covalently bonded crosslinks on the polybutadiene can beobtained. In the use of the inventive golf ball material as an injectionmolding material, component C must serve as the matrix and so it ispreferable for the ratio in which the polybutadiene as component B isblended, expressed as the weight ratio of component B to component C(B/C), to be set as appropriate within a range of 5/95 to 45/55. Eventhough the polybutadiene serving as component B is incorporated into thecomponent C matrix, golf ball materials obtained by the neutralizationreaction using component A have an excellent heat resistance.

If above component B is a polyacetal, it is preferable to use one ormore polyacetal selected from the group consisting of polyacetalhomopolymers and polyacetal copolymers having an impact strength (¼-inchnotched, at 23° C., ASTM D256) of 35 to 130 J/m and a flexural modulus(ASTM D790) of 2.50 to 3.10 GPa.

Specific examples of polyacetal homopolymers include Tenac 5050 andTenac 7010 (both available from Asahi Kasei Chemicals Corporation), andDelrin 500P (available from DuPont). Specific examples of polyacetalcopolymers include Amilus S731 and Amilus S761 (both available fromToray Industries, Inc.), Duracon M140S (available from Polyplastics Co.,Ltd.) and Tenac 7520 (available from Asahi Kasei Chemicals Corporation).Specific examples of comonomers that may be used in polyacetalcopolymers include alkylene oxides such as ethylene oxide and1,3-dioxolane.

The weight ratio of the polyacetal as component B to component C (B/C)is generally 50/50 to 1/99, and preferably 45/55 to 5/95. Too muchpolyacetal (B) may lower the compatibility of components B and C, inaddition to which the overall composition may becomes brittle and thedurability of golf balls obtained therewith may dramatically decrease.

Above component B is an essential ingredient for further enhancingspecific gravity control (specific gravity, ≧1.0), fatigue resistance,dimensional stability, wear resistance, impact resistance,processability, and the “feel” when hit (i.e., suitable hardness andflexural modulus), and so polyacetal is preferred because it hasexcellent fatigue resistance, dimensional stability, wear resistance,impact resistance, flexural modulus, thermal stability andprocessability. Polyacetal is desirable also as a hardness-increasingmaterial for imparting a higher hardness and, if it can be uniformlydispersed in component A, will provide an ionomer golf ball material ofa high hardness at an acid content of about 10 to 15 wt %.

In the practice of the invention, when component B is a thermosetpolymer, the weight ratio of components B and C (B/C) in the resultingacid-containing polymer composition is preferably adjusted within arange of 49/51 to 1/99.

Component C is preferably a polymer composition which has an acidcontent of 0.5 to 30 wt %, preferably 1.0 to 25 wt %, and is composed ofone or more selected from the group consisting of olefin-unsaturatedcarboxylic acid copolymers, olefin-unsaturated carboxylicacid-unsaturated carboxylic acid ester terpolymers, and polymerscontaining one or more monomer selected from the group consisting ofunsaturated carboxylic anhydrides, unsaturated dicarboxylic acids andunsaturated dicarboxylic acid half esters.

If component C is an olefin-unsaturated carboxylic acid bipolymer, theolefin is generally one having at least 2 carbons, but 8 or fewercarbons, and especially 6 or fewer carbons. Illustrative examples ofsuch olefins include ethylene, propylene, butene, pentene, hexene,heptene and octene. Ethylene is especially preferred. Illustrativeexamples of the unsaturated carboxylic acid include acrylic acid,methacrylic acid, maleic acid, maleic anhydride, and fumaric acid.Acrylic acid and methacrylic acid are especially preferred.

If component C is an olefin-unsaturated carboxylic acid-unsaturatedcarboxylic acid ester terpolymer, the unsaturated carboxylic acid esteris preferably a lower alkyl ester of the above-mentioned unsaturatedcarboxylic acids, specific examples of which include methylmethacrylate, ethyl methacrylate, propyl methacrylate, butylmethacrylate, methyl acrylate, ethyl acrylate, propyl acrylate and butylacrylate. The use of butyl acrylate (n-butyl acrylate, isobutylacrylate) is especially preferred.

If component C is selected from among polymers containing one or moremonomer selected from the group consisting of unsaturated carboxylicanhydrides, unsaturated dicarboxylic acids and unsaturated dicarboxylicacid half esters, examples of the unsaturated carboxylic anhydrideinclude maleic anhydride and itaconic anhydride, with maleic anhydridebeing especially preferred. Examples of the unsaturated dicarboxylicacid include maleic acid, fumaric acid and itaconic acid, and examplesof the unsaturated dicarboxylic acid half ester include monoesters ofthe foregoing dicarboxylic acids, such as the monoethyl ester of maleicacid, the monomethyl ester of fumaric acid and the monoethyl ester ofitaconic acid. The monoethyl ester of maleic acid is especiallypreferred.

Specific examples of above component C include unsaturated carboxylicanhydride, unsaturated dicarboxylic acid and/or unsaturated carboxylicacid-grafted polymers; unsaturated carboxylic anhydride, unsaturateddicarboxylic acid and/or unsaturated carboxylic acid-graftedolefin-unsaturated carboxylic acid polymers; unsaturated carboxylicanhydride, unsaturated dicarboxylic acid and/or unsaturated carboxylicacid-grafted olefin-unsaturated carboxylic acid ester polymers;unsaturated carboxylic anhydride, unsaturated dicarboxylic acid and/orunsaturated carboxylic acid-grafted olefin-unsaturated carboxylicacid-unsaturated carboxylic aid ester polymers; olefin-unsaturatedcarboxylic anhydride, unsaturated carboxylic acid ester polymers;olefin-unsaturated dicarboxylic acid-unsaturated carboxylic acid esterpolymers; and olefin-unsaturated dicarboxylic acid halfester-unsaturated carboxylic acid ester polymers.

Each of the above materials can be obtained by using a known method forcopolymerization and grafting. If the acid content within the copolymeris too low, the reactivity and strength (tensile strength at break) maydecrease. If it is too high, the processability may decrease.

Specific examples of commercial products that may be used as component Cinclude olefin-unsaturated carboxylic acid polymers such as Nucrel 960and Nucrel 2806 (both products of DuPont), and ESCOR 5200, ESCOR 5100and ESCOR 5000 (all products of Exxon-Mobil Chemical).

Specific examples of olefin-unsaturated carboxylic acid-unsaturatedcarboxylic acid ester polymers include Bynel 2002, Bynel 2014, Bynel2022 and Bynel E403 (all products of DuPont), and ESCOR ATX325, ESCORATX320 and ESCOR ATX310 (all products of Exxon-Mobil Chemical).

Specific examples of unsaturated carboxylic anhydride polymers includeMODIPER A8100, MODIPER A8200 and MODIPER A8400 (all products of NORCorporation), and LOTADER 3200, LOTADER 3300, LOTADER 5500, LOTADER6200, LOTADER 7500, LOTADER 8200 and LOTADER TX8030 (all products ofATOFINA).

Specific examples of commercial unsaturated carboxylic anhydride graftedpolymers that may be used include Polybond 3009, Polybond 3200 andRoyaltough 498 (all products of Uniroyal Chemical), ADOMER NF518 andADOMER QE800 (both products of Mitsui Chemicals, Inc.), Bynel 2167,Bynel 2174, Bynel 4206, Bynel 4288, Bynel 50E561 and Bynel 50E571 (allproducts of DuPont), and Exxelor VA1801, Exxelor VA1803, Exxelor VA1840and Exxelor P01020 (all products of Exxon-Mobil Chemical).

In addition, any additive suitable for the intended use may be includedin the golf ball material of the invention. If the golf ball material ofthe invention is to be used as a cover material, additives such aspigments, dispersants, antioxidants, ultraviolet absorbers and lightstabilizers may be included together with above components A to C. Whenthese additives are included, the amount of addition thereof per 100parts by weight of components A to C combined is generally at least 0.1part by weight, and preferably at least 0.5 part by weight, butgenerally not more than 10 parts by weight, and preferably not more than4 parts by weight.

The golf ball material of the invention has a specific gravity ofgenerally at least 0.9, preferably at least 0.92, and more preferably atleast 0.94, but generally not more than 1.3, preferably not more than1.2, and more preferably not more than 1.05.

The golf ball of the invention is a golf ball which includes as anessential component therein a molding made from the inventive golf ballmaterial. Moldings made from the above-described golf ball material maybe used as part or all of the golf ball. Examples include the cover ofthread-wound golf balls in which the cover has a single-layer structureor a multilayer structure of two or more layers; one-piece golf balls;the solid core or cover of two-piece solid golf balls; and the solidcore, intermediate layer or cover of multi-piece solid golf balls suchas three-piece solid golf balls. The inventive golf ball is not subjectto any particular limitation, provide it is a golf ball which includesas an essential component therein a molding of the inventive golf ballmaterial.

It is particularly advantageous for the golf ball material of theinvention to be used as the cover material in a two-piece solid golfball composed of a core and a cover which encloses the core, or as thecover material or intermediate layer material in a multi-piece solidgolf ball composed of a core of at least one layer, at least oneintermediate layer which encloses the core, and at least one cover whichencloses the intermediate layer.

Two-piece solid golf balls with a butadiene rubber core and a coverinjection-molded from the golf ball material prepared by theabove-described method were fabricated and tested, from which it wasfound that golf balls having the following performance and effects canbe obtained. The results indicated below were obtained by comparing theinvention with, as a control, a golf ball in which the cover materialwas a melt mixture of a metal ion species-containing ionomer of the samedegree of neutralization (equivalent to the resin composition ofcomponents A and C) with component B.

-   -   a) The cover surface had an excellent uniformity.    -   b) Excellent scuff resistance.    -   c) Excellent durability (number of shots).    -   d) High hardness.    -   e) Excellent heat resistance.    -   f) Partially interpenetrating network structure.

EXAMPLES

Examples are given below by way of illustration and not by way oflimitation. The twin-screw extruder for neutralization used in theinvention had a screw diameter of 32 mm, an overall L/D ratio of 41, andan L/D ratio for the kneading disc zone which was 40% of the overall L/Dratio.

Example 1

A 5-liter pressure kneader (manufactured by Naniwa MachineryManufacturing Co., Ltd.; temperature setting, 100° C.) was employed. Thebase polymer for the master batch was A-C580/Nucrel 599 blended in aweight ratio of 30/70, and the zinc oxide designated below as ZnO-2(average particle size, 0.6 μm) was used. The kneader was charged with acombined amount of 2.0 kg of the A-C580/Nucrel 599 and the ZnO-2 in a50/50 ratio by weight, and mixing was carried out for 20 minutes underan applied pressure of 0.49 MPa at a rotor speed of 35 rpm and at mixingtemperature controlled within a range of 120 to 130° C. The mixture wasdischarged as a strand from a 40 mm diameter twin-screw/single-screwextruder (Naniwa Machinery Manufacturing Co., Ltd.; temperature setting,180° C.), passed through a cooling water bath and by an air knife, thenwas rendered into pellets by a pelletizer. The melt flow rate of theresulting ZnO-2 master batch having a ZnO-2 content of 50 wt % was 2.1g/10 min (measured at 190° C. under a load of 2,160 g). This masterbatch is designated below as ZnO-2 MB.

A-C580: A polyethylene wax produced by Tomen Plastics Corporation.Acrylic acid content, 9.6 wt %; viscosity, 650 cps at 140° C. Nucrel599: An ethylene-methacrylic acid polymer produced by DuPont.Methacrylic acid content, 10 wt %; MFR, 450 g/10 min.

Example 2

A golf ball material was prepared using the components and proportionsshown in Table 1. Aside from charging the 5-liter pressure kneader witha combined amount of 2.5 kg of BR01 and EMAA-1 in the indicatedproportions and using a temperature setting of 80° C., operation of thekneader was carried out as in Example 1. The mixed material was thenremoved and, except for a temperature setting of 130° C., operation of atwin-screw/single-screw extruder was carried out in the same way as inExample 1. Pellets of the resulting BR01/EMAA-1 mixture and ZnO-1 wereseparately fed to the hopper of a twin-screw extruder (temperaturesetting, 160° C.) in the specific proportions indicated in Table 1. Meltmixing was then carried out at a screw speed of 70 rpm and an extrusionrate of 16 kg/h while using a pump for the pressurized injection of aliquid to inject water in an amount of 2 wt %, based on the resinextrusion rate, at an intermediate point along the twin-screw extruder,and while releasing volatiles through a vacuum vent. Next, the stranddischarged from the extruder die was passed through a cooling waterbath, then excess water was removed with an air knife, after which thestrand was pelletized by a pelletizer, yielding a uniform composition.Pellets of the uniform, transparent composition thus obtained were usedto form a 3 mm thick sheet having a length and width of 150 mm each in ahot press molding machine. The sheet was visually examined, and found tobe free of ZnO-1 in unreacted form or as undispersed masses. Theproperties of the resulting golf ball material were then evaluated. Theresults are shown in Table 1.

Example 3

Aside from using the ZnO-2 MB prepared in Example 1 instead of ZnO-1, auniform and transparent BR01/EMAA-1/ZnO-2 MB composition was obtained byrepeating the operations in Example 2 using the proportions indicated inTable 1. Pellets of the resulting uniform, transparent composition wereused to form a 3 mm thick sheet having a length and width of 150 mm eachin a hot press molding machine. The sheet was visually examined, andfound to be free of ZnO-2 in unreacted form or as undispersed masses.The properties of the resulting golf ball material were then evaluated.The results are shown in Table 1.

Comparative Example 1

Aside from using ZnO-2 instead of a ZnO-2 master batch, the sameoperations as in Example 2 were repeated using the proportions indicatedin Table 1. Pellets of the resulting BR01/EMAA-1/ZnO-2 composition wereused to form a 3 mm thick sheet having a length and width of 150 mm eachin a hot press molding machine. The sheet was visually examined,confirming the presence of a large amount of unreacted ZnO-2 (whitespecks). The properties of the resulting golf ball material were thenevaluated. The results are shown in Table 1.

TABLE 1 Comparative Example 2 Example 3 Example 1 BR01 10_((2nd))10_((2nd)) 10_((2nd)) EMAA-1 90_((1st)) 90_((1st)) 90_((1st)) ZnO-13_((3rd)) — — ZnO-2MB — 6_((3rd)) — ZnO-2 — — 3_((3rd)) MFR (g/10 min)21 24 170 Hardness (Shore D), 23° C. 52 52 40 Rebound (%) θ₀ = 40° 40 4026 θ₀ = 80° 30 30 21 UTS (MPa) 17.5 17.9 11.2 UTE (%) 187 200 248Remarks Transparent Translucent Amounts of components are given in partsby weight. Numbers in parentheses ( ) indicate the mixing order.

The properties obtained with the use of ZnO-1 in Example 1 and with theuse of ZnO-2 MB in Example 2 were substantially the same. Compared withthese examples according to the invention, the properties with the useof ZnO-2 in the comparative example were inferior, and included a highMFR, a low hardness and a low rebound.

BR01: The polybutadiene BR01 produced by JSR Corporation; cis-1,4 bondcontent, 96%; nickel polymerization catalyst. BR02: A product preparedby mixing 2 parts by weight of maleic anhydride with 100 parts by weightof BR01, then adding 1 part by weight of dicumyl peroxide per 100 partsby weight of the mixture and mixing at about 80° C. for 10 minutes.ZnO-1: Available from Sakai Chemical Industry Co., Ltd. Nanofine-50, azinc oxide having an average particle size of 20 nm and a particle sizedistribution of 1 to 100 nm. Proportion of component with particle size≦0.05 μm, about 60%. ZnO-2: A type of zinc oxide produced by SakaiChemical Industry Co., Ltd. Average particle size, 0.8 μm. Particle sizedistribution, 0.07 to 3.00 μm. POM: Amilus S761, produced by TorayCorporation. MFR, 9.6 g/10 min; melting point, 166° C.; Rockwellhardness, R115. EMAA-1: Nucrel 2050H, an ethylene-methacrylic acidcopolymer produced by DuPont-Mitsui Polychemicals Co., Ltd. MFR, 500g/10 min. EMAA-2: Nucrel 1560, an ethylene-methacrylic acid copolymerproduced by DuPont-Mitsui Polychemicals Co., Ltd. MFR, 60 g/10 min.S8940: Sodium ionomer of an ethylene-methacrylic acid copolymer,produced by DuPont. MFR, 3.0 g/10 min. MFR (g/10 min): The melt flowrate was measured in accordance with JIS-K7210 at a test temperature of190° C. and a test load of 21.18 N (2.16 kgf). Shore D Hardness:Measured in accordance with ASTM D-2240. Rebound Resilience: A valuemeasured in accordance with JIS-K6255 and ISO 4662 using a Tripsonrebound resilience tester. Elongation at Measured in accordance withJIS-K7161. Break (%) and Tensile Strength (MPa):

It is apparent from the above data that when the metal ionic species(ZnO-2) is added directly in the form of merely fine (rather thanultrafine) particles, neutralization of the acids within theacid-containing polymer cannot easily be brought to completion, andmoreover that several passes through the extruder are required to bringthe neutralization reaction to completion. These results confirm theimportance of using a metal ionic species in the form of ultrafineparticles (ZnO-1) or as a master batch (ZnO-2 MB). Methods for preparingthe golf ball material using ZnO-1 and ZnO-2 MB and the properties ofgolf ball materials thus obtained are evaluated below.

Example 4

Aside from using BR02 instead of BR01 and changing the temperaturesetting of the twin-screw extruder from 160° C. to 180° C., a uniformBR02/EMAA-1/ZnO-1 mixed composition was obtained by formulating thecomponents as shown in Table 2 and repeating the same operations as inExample 2. Pellets of the resulting uniform and transparent compositionwere used to form a 3 mm thick sheet having a length and width of 150 mmeach in a hot press molding machine. The sheet was visually examined andfound to be free of ZnO-1 in unreacted form or as undispersed masses.The properties of the resulting golf ball material were then evaluated.The results are shown in Table 2.

Example 5

POM and EMAA-1 were dry blended in the proportions shown in Table 2, fedto the hopper of the twin-screw extruder (temperature setting, 180° C.)used in Example 2, and melt-mixed at a screw speed of 80 rpm, anextrusion rate of 20 kg/h and with the release of volatiles through avacuum vent. The strand discharged from the extruder die was passedthrough a cooling water bath, after which excess water was removed withan air knife, then the strand was pelletized by a pelletizer, yielding auniform POM/EMAA-1 mixture. Aside from dry-blending this POM-EMAA-1mixture with ZnO-2 MB in the proportions shown in Table 2 instead of aBR01/EMAA-1 mixture with ZnO-1, and changing the temperature settingfrom 160° C. to 190° C., the same twin-screw extruder operations as inExample 2 were repeated, giving a uniform POM/EMAA-1/ZnO-2 MBcomposition. Pellets of the resulting uniform and transparentcomposition were used to form a 3 mm thick sheet having a length andwidth of 150 mm each in a hot press molding machine. The sheet wasvisually examined and found to be free of ZnO-2 in unreacted form or asundispersed masses. The properties of the resulting golf ball materialwere then evaluated. The results are shown in Table 2.

Example 6

Aside from using EMAA-2 instead of EMAA-1 and using ZnO-1 instead ofZnO-2 MB, a uniform POM/EMAA-2/ZnO-1 composition was obtained byformulating the components as shown in Table 2 and repeating the sameoperations as in Example 5. Pellets of the resulting uniform andtransparent composition were used to form a 3 mm thick sheet having alength and width of 150 mm each in a hot press molding machine. Thesheet was visually examined and found to be free of ZnO-2 in unreactedform or as undispersed masses. The properties of the resulting golf ballmaterial were then evaluated. The results are shown in Table 2.

Example 7

The POM/EMAA-2/ZnO-1 composition obtained in Example 6 and S8940 weredry blended in the proportions shown in Table 2, fed to the hopper ofthe twin-screw extruder used in Example 2 (temperature setting, 190°C.), and melt-mixed at a screw speed of 80 rpm, an extrusion rate of 20kg/h, and while releasing volatiles through a vacuum vent. The stranddischarged from the extruder die was passed through a cooling waterbath, after which excess water was removed with an air knife, then thestrand was pelletized by a pelletizer, yielding a uniformPOM/EMAA-2/ZnO-1/S8940 composition. The properties of the resulting golfball material were then evaluated. The results are shown in Table 2.

Comparative Example 2

A uniform EMAA-1/ZnO-1 mixture in which a neutralization reaction hadtaken place between the EMAA-1 and ZnO-1 was obtained by extrusion in atwin-screw extruder under the same conditions as in Example 4(temperature setting, 180° C.; pressurized injection of water). Theresulting mixture was dry-blended with BR02 in the proportions shown inTable 2, then melt-mixed under the twin-screw extruder conditions forPOM/EMAA-1 in Example 5 (temperature setting, 180° C.) and pelletized,yielding a non-uniform EMAA-1/ZnO-1/BR02 composition. The properties ofthe resulting golf ball material were then evaluated. The results areshown in Table 2.

Comparative Example 3

A uniform EMAA-1/ZnO-2 MB mixture in which a neutralization reaction hadtaken place between the EMAA-1 and ZnO-2 MB was obtained by extrusion ina twin-screw extruder under the same conditions as in Example 4(temperature setting, 180° C.; pressurized injection of water). Theresulting mixture was dry-blended with POM in the proportions shown inTable 2, then melt-mixed under the twin-screw extruder conditions inExample 7 (temperature setting, 190° C.) and pelletized, yielding acloudy, non-uniform EMAA-1/ZnO-2 MB/POM composition. The properties ofthe resulting golf ball material were then evaluated. The results areshown in Table 2.

Comparative Example 4

A uniform EMAA-2/ZnO-1 mixture in which a neutralization reaction hadtaken place between the EMAA-2 and ZnO-1 was obtained by extrusion in atwin-screw extruder under the same conditions as in Example 4(temperature setting, 180° C.; pressurized injection of water). Theresulting mixture was dry-blended with POM in the proportions shown inTable 2, then melt-mixed under the twin-screw extruder conditions inExample 7 (temperature setting, 190° C.) and pelletized, yielding acloudy, non-uniform EMAA-2/ZnO-1/POM composition. The properties of theresulting golf ball material were then evaluated. The results are shownin Table 2.

Comparative Example 5

The cloudy, non-uniform EMAA-2/ZnO-1/POM composition obtained inComparative Example 4 was dry-blended with S8940 in the proportionsindicated in Table 2, then melt-mixed under the twin-screw extruderconditions in Example 7 (temperature setting, 190° C.) and pelletized,yielding a cloudy, non-uniform EMAA-2/ZnO-1/POM/S8940 composition. Theproperties of the resulting golf ball material were then evaluated. Theresults are shown in Table 2.

Reference Example

Aside from not including the BR02 or POM used in the above examples,using EMAA-1 and ZnO-1 in the proportions shown in Table 2, and changingthe temperature setting of the twin-screw extruder from 160° C. to 180°C., a uniform and transparent EMAA-1/ZnO-1 composition was obtainedunder the same extrusion conditions as in Example 2. The properties ofthe resulting golf ball material were evaluated.

TABLE 2 Example Comparative Example Reference 4 5 6 7 2 3 4 5 ExamplePOM — 10_((2nd)) 10_((2nd)) 10_((2nd)) — 10_((3rd)) 10_((3rd))10_((3rd)) — S8940 — — — 100_((4th)) — — — 100_((4th)) — BR02 10_((2nd))— — — 10_((3rd)) — — — — EMAA-1 90_((1st)) 90_((1st)) — — 90_((1st))90_((1st)) — — 100 EMAA-2 — — 90_((1st)) 90_((1st)) — — 90_((1st))90_((1st)) — ZnO-1 3_((3rd)) — 3.8_((3rd)) 3.8_((3rd)) 3_((2nd)) —3.8_((2nd)) 3.8_((2nd)) 3_((3rd)) ZnO-2MB — 6_((3rd)) — — — 6_((2nd)) —— — MFR (g/10 min) 9.0 29.6 2.4 2.6 20.4 26.5 1.7 2.1 40.9 Hardness(Shore D), 23° C. 54 66 66 66 41-53 64 64 65 62 Rebound (%) θ₀ = 40° 4039 43 — 40 39 43 — 40 θ₀ = 80° 30 29 34 — 30 29 35 — 30 UTS (MPa) 18.919.0 27.8 33.0 Broke 18.5 27.5 31.8 21.2 UTE (%) 236 161 309 341 Broke174 314 386 279 Remarks Transparent Cloudy, translucent Amounts ofcomponents are given in parts by weight. Numbers in parentheses ( )indicate the mixing order.

On comparing the results obtained in Examples 4 to 7 with the resultsobtained in the respective corresponding Comparative Examples 2 to 5, itis apparent that the golf ball materials obtained in the examplesaccording to the invention were uniform mixtures, and tended in eachcase to have a higher hardness and tensile strength. Also, when POM,which has a linear structure, was included, the inventive golf ballmaterials had a high melt flow rate and did not exhibit a loss ofrebound resilience. Moreover, the inventive golf ball materialsgenerally tended to have a higher hardness than the material obtained inthe reference example.

Golf balls were produced using the above materials and evaluated todetermine whether these characteristics are reflected in the performanceof the golf ball.

Examples 8 to 10

Using the materials obtained in Examples 4, 6 and 7 as the covermaterials in two-piece golf balls, using a crosslinked butadiene rubberbody (diameter, 38.9 mm; weight, 36.0 g; compressive strain, 3.35 mm) asthe core, and using an injection molding machine (temperature settings:hopper, 160° C.; C1 to head, 180 to 200° C.), the cover material wasinjection molded over the core at a molding pressure of 5.9 MPa, a dwellpressure of 4.9 MPa, an injection and dwell time of 8 seconds, and acooling time of 25 seconds, thereby producing two-piece golf balls(diameter, 42.7 mm; weight, 45.5 g). These golf balls were thenevaluated. The results are shown in Table 3.

Comparative Examples 6 to 8

These comparative examples correspond respectively to above Examples 8,9 and 10. The golf ball materials prepared in Comparative Examples 2, 4and 5 were used as the cover materials for two-piece golf balls, andtwo-piece golf balls were produced under the same injection moldingconditions as in Examples 8 to 10. These golf balls were then evaluated.The results are shown in Table 3.

TABLE 3 Example Comparative Example 8 9 10 6 7 8 Golf ball cover EX 4 EX6 EX 7 CE 2 CE 4 CE 5 material material material material materialmaterial material Deflection hardness 2.91 2.77 2.73 2.46 2.80 2.74 (mm)*1 GB facial hardness *2 64 70 70 59 70 70 Initial  0° 76.48 76.04 76.2976.31 76.06 76.22 velocity 23° 76.49 76.76 77.38 76.42 76.76 77.32 (m/s)*3 40° 75.79 76.57 77.23 75.78 76.54 77.23 C.O.R. *4 0.770 0.775 0.7920.768 0.774 0.791 Number of shots 87 85 103 22 80 90 (Durability) *5Scuff resistance, Good Good Good Poor Poor Good 23° C. *6 Abrasionresistance Good Good Good Poor Poor Good (Sand) *7 Remarks Good heatGood heat Good Poor heat Poor heat Poor resistance resistance durabilityresistance resistance durability Good durability Poor durabilty GoodUniformity Poor Uniformity *1 Deflection hardness The amount ofdeflection by the spherical object being tested when subjected, on ahard plate, to an increase in load from an initial load state of 98 N(10 kgf) to a load of 1,275 N (130 kgf). *2 GB facial hardness Shore Dhardness on the ball surface. The measurement was carried out using atype D durometer in accordance with ASTM-2240. *3 Initial velocity It isnoted that the initial velocity was measured using the same type ofinitial velocity instrument as the USGA rotary drum initial velocityinstrument approved by R&A. The ball was conditioned at a temperature of23 ± 1° C. for at least 3 hours and tested in a chamber at roomtemperature of 23 ± 2° C. The ball was hit with a head having a strikingmass of 250 pounds (113.4 kg) at a hitting speed of 143.8 ft/s (43.83m/s). One dozen of balls were hit each four times, and the time ofpassage across a distance of 6.28 feet (1.91 m) was measured, from whichthe initial velocity was computed. This cycle was completed within about15 minutes. *4 C.O.R. Coefficient of restitution (C.O.R.) was measuredby firing a golf ball in an air cannon at a velocity of 43 m/sec againsta steel plate. The rebound velocity was then measured. The reboundvelocity was divided by the forward velocity to give a coefficient ofrestitution. *5 Number of shots (Durability) The durability of each golfball was evaluated using an ADC Ball COR Durability Tester produced byAutomated Design Corporation (U.S.). This tester has the ability to firea golf ball using air pressure and cause it to repeatedly strike twometal plates arranged in parallel. The number of firings needed until aball cracks was treated as the indicator of durability. Velocity ofimpact with metal plate: 43 m/s Number of runs (N): 7 Type: HorizontalCOR *6 Scuff resistance After the balls were held at 23° C., they werenormally hit for each ball by means of a swing robot equipped with apitching wedge at a head speed of 33 m/s. The scuff by hit was observedand was evaluated according to the criterion below. Good: None of scuffor slight scuff as not cared when the ball is used Poor: fluff on ballsurface or scuff as lack of dimples *7 Abrasion resistance 15 golf ballswith a 1.7-litter volume of sand were put in a 5-litter cylindricalcontainer and laid down to turn round at a 50 rotation per minute speedfor 2 hours. After the procedure, the golf balls were picked up andobserved.

On comparing Example 8 with Comparative Example 6, Example 9 withComparative Example 7, and Example 10 with Comparative Example 8, it isapparent that the golf balls obtained in the examples according to theinvention had much better durability (number of shots), cut resistance,scuff or abrasion resistance, and heat resistance during injectionmolding. Moreover, the initial velocity and coefficient of restitutionin each case remained about the same.

Japanese Patent Application No. 2004-228901 is incorporated herein byreference.

Although some preferred embodiments have been described, manymodifications and variations may be made thereto in light of the aboveteachings. It is therefore to be understood that the invention may bepracticed otherwise than as specifically described without departingfrom the scope of the appended claims.

1. A golf ball material comprising: (A) a metal ionic species in a formof (A1) ultrafine particles of an oxygen-containing inorganic metalcompound having an average size of 0.005 to 0.1 μm and a particle sizedistribution of 0.001 to 1.0 μm in diameter, (B) at least one polymerselected from the group consisting of diene polymers, thermoplasticpolymers and thermoset polymers, and (C) at least one acid-containingpolymer having an acid content of 0.5 to 30% by weight and selected fromthe group consisting of olefin-unsaturated carboxylic acid copolymers,olefin-unsaturated carboxylic acid-unsaturated carboxylic acid esterterpolymers, and polymers containing one or more monomer selected fromthe group consisting of unsaturated carboxylic anhydrides, unsaturateddicarboxylic acids and half esters thereof, the component (C) beingun-neutralized; which is obtained by blending and melt-mixing componentB and component C to form a molten polymer composition of components Band C, then blending component A into the molten polymer composition inwhich at least some of the acid groups present in components B and C ofthe polymer composition are neutralized.
 2. The golf ball material ofclaim 1, wherein component B is at least one polymer selected from thegroup consisting of polyolefin elastomers, polystyrene elastomers,polyacrylate polymers, polyamide elastomers, polyurethane elastomers,polyester elastomers, diene polymers, polyacetals, epoxy resins,unsaturated polyester resins, silicone resins and ABS resins.
 3. Thegolf ball material of claim 1, wherein component B and component C areblended together in a weight ratio B/C of 99/1 to 1/99.
 4. The golf ballmaterial of claim 1, wherein component B is a thermoset polymer, andcomponents B and C are blended together in a weight ratio B/C of 49/51to 1/99.
 5. The golf ball material of claim 1, wherein component B is apolyacetal homopolymer or copolymer or both having an impact strength of35 to 130 J/m and a flexural modulus of 2.50 to 3.10 GPa.
 6. The golfball material of claim 1, wherein component B is a polyacetal andcomprises between 1 to 50% by weight of the combined weight of componentB and component C in the polymer blend.
 7. The golf ball material ofclaim 1, wherein component A1 is blended together with the polymer blendof component B and component C in an amount equivalent to a desireddegree of neutralization of the acid groups in the polymer blend ofcomponents B and C.
 8. A golf ball comprising a part made of the golfball material of claim
 1. 9. A golf ball wherein the golf ball materialof claim 1 is used as a cover material in a two-piece solid golf ballcomposed of a core and a cover surrounding the core.
 10. A golf ballwherein the golf ball material of claim 1 is used as a cover material oran intermediate layer material in a multi-piece solid golf ball composedof a core of at least one layer, at least one intermediate layersurrounding the core, and at least one cover surrounding theintermediate layer.
 11. The golf ball material of claim 1, wherein theparticulate oxygen-containing inorganic metal compound (A1) is at leastone type selected from the group consisting of lithium carbonate, sodiumcarbonate, potassium carbonate, magnesium carbonate, calcium carbonate,magnesium oxide, zinc oxide and calcium oxide.
 12. A golf ball materialcomprising: (A) a metal ionic species in at least one form selected fromthe group consisting of (A1) ultrafine particles and (A2) a masterbatch, (B) a polybutadiene having a cis-1,4 bond content of at least60%, a 1,2-vinyl bond content of at most 4%, a Mooney viscosity (ML₁₊₄(100°C.)) of 35 to 65, a weight-average molecular weight (Mw) of 450,000to 850,000, and a weight-average molecular weight (Mw) to number-averagemolecular weight (Mn) ratio of at most 5, and (C) at least oneacid-containing polymer having an acid content of 0.5 to 30% by weightand selected from the group consisting of olefin-unsaturated carboxylicacid copolymers, olefin-unsaturated carboxylic acid-unsaturatedcarboxylic acid ester terpolymers, and polymers containing one or moremonomer selected from the group consisting of unsaturated carboxylicanhydrides, unsaturated dicarboxylic acids and half esters thereof, thecomponent (C) being un-neutralized; which is obtained by blending andmelt-mixing component B and component C to form a molten polymercomposition of components B and C, then blending component A into themolten polymer composition in which at least some of the acid groupspresent in components B and C of the polymer composition areneutralized.
 13. The golf ball material of claim 12, wherein thepolybutadiene is used itself or in a composition of an acid anhydrideand a radical crosslinking agent.
 14. The golf ball material of claim12, wherein component B comprises between 1 to 50% by weight of thecombined weight of component B and component C in the polymer blend. 15.The golf ball material of claim 12, wherein the metal ionic species ofcomponent A is in the form of (A1) ultrafine particles of anoxygen-containing inorganic metal compound having an average size of0.005 to 0.1 μm and a particle size distribution of 0.001 to 1.0 μm indiameter.
 16. The golf ball material of claim 15, wherein theparticulate oxygen-containing inorganic metal compound (A1) is at leastone type selected from the group consisting of lithium carbonate, sodiumcarbonate, potassium carbonate, magnesium carbonate, calcium carbonate,magnesium oxide, zinc oxide and calcium oxide.
 17. The golf ballmaterial of claim 8, wherein component A1 or component A2 or both areblended together with the polymer blend of component B and component Cin an amount equivalent to a desired degree of neutralization of theacid groups in the polymer blend of components B and C.
 18. A golf ballcomprising a part made of the golf ball material of claim
 12. 19. A golfball wherein the golf ball material of claim 12 is used as a covermaterial in a two-piece solid golf ball composed of a core and a coversurrounding the core.
 20. A golf ball wherein the golf ball material ofclaim 12 is used as a cover material or an intermediate layer materialin a multi-piece solid golf ball composed of a core of at least onelayer, at least one intermediate layer surrounding the core, and atleast one cover surrounding the intermediate layer.